JP5142139B2 - Blue-violet light blocking glass - Google Patents
Blue-violet light blocking glass Download PDFInfo
- Publication number
- JP5142139B2 JP5142139B2 JP2007545250A JP2007545250A JP5142139B2 JP 5142139 B2 JP5142139 B2 JP 5142139B2 JP 2007545250 A JP2007545250 A JP 2007545250A JP 2007545250 A JP2007545250 A JP 2007545250A JP 5142139 B2 JP5142139 B2 JP 5142139B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass
- blue
- silver
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011521 glass Substances 0.000 title claims description 196
- 230000000903 blocking effect Effects 0.000 title claims description 68
- 235000005811 Viola adunca Nutrition 0.000 title claims description 65
- 240000009038 Viola odorata Species 0.000 title claims description 65
- 235000013487 Viola odorata Nutrition 0.000 title claims description 65
- 235000002254 Viola papilionacea Nutrition 0.000 title claims description 65
- -1 copper (I) halide Chemical class 0.000 claims description 76
- 229910052760 oxygen Inorganic materials 0.000 claims description 66
- 229910052709 silver Inorganic materials 0.000 claims description 61
- 239000004332 silver Substances 0.000 claims description 58
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 34
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 29
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 28
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 28
- 238000002834 transmittance Methods 0.000 claims description 28
- 229910052792 caesium Inorganic materials 0.000 claims description 27
- 229910052701 rubidium Inorganic materials 0.000 claims description 27
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 26
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 26
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 24
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 23
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 20
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 15
- 229910001431 copper ion Inorganic materials 0.000 claims description 15
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 13
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 13
- 239000004973 liquid crystal related substance Substances 0.000 claims description 11
- 229940100890 silver compound Drugs 0.000 claims description 11
- 150000003379 silver compounds Chemical class 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 18
- 239000005749 Copper compound Substances 0.000 description 12
- 150000001880 copper compounds Chemical class 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 150000001879 copper Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000010946 fine silver Substances 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910008355 Si-Sn Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910006453 Si—Sn Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 231100000040 eye damage Toxicity 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 230000037380 skin damage Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/226—Glass filters
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/005—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to introduce in the glass such metals or metallic ions as Ag, Cu
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/16—Microcrystallites, e.g. of optically or electrically active material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
- C03C2217/284—Halides
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2203/00—Function characteristic
- G02F2203/05—Function characteristic wavelength dependent
- G02F2203/055—Function characteristic wavelength dependent wavelength filtering
Description
本発明は、青紫光遮断ガラスに関する。 The present invention relates to a blue-violet light blocking glass.
ガラスを用いた光の遮断方法は、干渉型と吸収型とに大別できる。 The light blocking method using glass can be roughly divided into an interference type and an absorption type.
干渉型は、紫外域又は可視域の光を吸収しないガラスに多層膜を蒸着し、多層膜による光の干渉を利用することにより、一定波長領域の光を遮断する方法である。 The interference type is a method of blocking light in a certain wavelength region by depositing a multilayer film on glass that does not absorb light in the ultraviolet region or visible region, and utilizing light interference by the multilayer film.
干渉型の遮断方法には入射角依存性があるため、ガラスに対して垂直方向に入射された一定波長領域の光は遮断できるが、他の角度からの入射光は遮断できない欠点がある。また、干渉型の遮断方法では、ＪＩＳ Ｂ ７１１３に規定の波長傾斜幅（Δλ）が大きく、シャープな遮断効果が得られ難い。 Since the interference-type blocking method has an incident angle dependency, light in a certain wavelength region incident in a direction perpendicular to the glass can be blocked, but incident light from other angles cannot be blocked. Further, in the interference type blocking method, the wavelength inclination width (Δλ) defined in JIS B 7113 is large, and it is difficult to obtain a sharp blocking effect.
吸収型は、光を吸収するイオン、金属コロイド、半導体微粒子等をガラス中に含有することにより、一定波長領域の光を遮断する方法である。特に半導体微粒子は、吸収機能が良好である。 The absorption type is a method of blocking light in a certain wavelength region by containing light absorbing ions, metal colloids, semiconductor fine particles, and the like in glass. In particular, semiconductor fine particles have a good absorption function.
半導体微粒子としては、例えば、ＩＩ〜ＶＩ族化合物半導体であるＣｄＳ、ＣｄＳｅ、ＣｄＳＳｅ等のＣｄ化合物微結晶が知られている。しかしながら、Ｃｄ化合物は有害物質であり、バッチ調合、運搬、溶融等の工程において作業者の健康を害する危険性がある。また、ガラスの切断、研削、研磨等の加工の際に出る排水及び廃棄物中に含まれるＣｄ化合物の処理にも労力を要する。更に、上記Ｃｄ化合物を含有したガラスの中には、透過率５０％の値が波長４５０ｎｍ以上に示されるものがあるが、波長傾斜幅（Δλ）が大きく、干渉型と同様にシャープな遮断効果が得られ難い。 As the semiconductor fine particles, for example, Cd compound microcrystals such as CdS, CdSe, CdSSe which are II to VI group compound semiconductors are known. However, Cd compounds are harmful substances, and there is a risk of harming workers' health in processes such as batch preparation, transportation, and melting. In addition, labor is also required for the treatment of Cd compounds contained in waste water and waste generated during processing such as cutting, grinding, and polishing of glass. Furthermore, some of the glasses containing the Cd compound have a transmittance value of 50% at a wavelength of 450 nm or more, but have a large wavelength inclination width (Δλ) and a sharp blocking effect similar to the interference type. Is difficult to obtain.
上記Ｃｄ化合物をＺｎ微粒子に置換することにより、特定波長領域の光を吸収する遮断技術は、例えば、特許文献１に記載されている。しかしながら、特許文献１に記載された遮断技術は波長傾斜幅（Δλ）が依然として大きく、シャープな遮断効果は得られ難い。 For example, Patent Document 1 discloses a blocking technique that absorbs light in a specific wavelength region by replacing the Cd compound with Zn fine particles. However, the cutoff technique described in Patent Document 1 still has a large wavelength gradient width (Δλ), and it is difficult to obtain a sharp cutoff effect.
他方、半導体微粒子としてＩ〜ＶＩＩ族半導体のハロゲン化銅（Ｉ）微粒子を用いた、紫外線遮断ガラス及び着色ガラスが知られている（特許文献２〜８）。 On the other hand, ultraviolet blocking glass and colored glass using copper (I) halide fine particles of Group I to VII semiconductor as semiconductor fine particles are known (Patent Documents 2 to 8).
ハロゲン化銅（Ｉ）微粒子としては、例えば、ＣｕＣｌ、ＣｕＢｒ、ＣｕＩ等の化合物又はこれらの混合物が知られている。これらのハロゲン化銅（Ｉ）微粒子は、有害でなく容易に使用できる。また、当該微粒子を含有する紫外線遮断ガラス及び着色ガラスは、波長傾斜幅（Δλ）が狭く、シャープな遮断機能を有する。 As the copper (I) halide fine particles, for example, compounds such as CuCl, CuBr, and CuI or mixtures thereof are known. These copper (I) halide fine particles are not harmful and can be used easily. Further, the ultraviolet blocking glass and the colored glass containing the fine particles have a narrow wavelength inclination width (Δλ) and a sharp blocking function.
しかしながら、ハロゲン化銅（Ｉ）微粒子を含有する上記ガラスは、微粒子の組成、微粒子含有量等を調整しても、可視光線の高透過率（厚さ１ｍｍのガラス板に波長３００〜６００ｎｍの光を入射した場合に、４５０〜６００ｎｍの平均透過率が８５％以上）を維持したい場合には、透過率５０％の値は最大でも４３０ｎｍ止まりであり、更に長波長の４３０〜４５０ｎｍの光を十分に遮断することができない。従って、４５０ｎｍ付近でのシャープな遮断機能の発現が望まれている。
本発明は、ハロゲン化銅（Ｉ）微粒子を含有するガラスであって、波長４５０〜６００ｎｍの光を十分に透過し、４５０ｎｍよりも短波長の光をシャープに遮断する青紫光遮断ガラスを提供することを目的とする。 The present invention provides a glass containing copper (I) halide fine particles that sufficiently transmits light having a wavelength of 450 to 600 nm and sharply blocks light having a wavelength shorter than 450 nm. For the purpose.
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、ハロゲン化銅（Ｉ）微粒子に加えて銀を含有する場合には上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved when silver is contained in addition to the copper (I) halide fine particles, and the present invention has been completed. It was.
即ち、本発明は、下記の青紫光遮断ガラスに係る。
１． ハロゲン化銅（Ｉ）及び銀を含有する、青紫光遮断ガラス。
２． ＳｉＯ２：２０〜８５重量％、Ｂ２Ｏ３：２〜７５重量％、Ａｌ２Ｏ３：１０重量％以下、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種：２〜３０重量％、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種：１〜１５重量％、ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種：１０重量％以下、Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種：５重量％以下、ＳｎＯ２：５重量％以下、ハロゲン化銅（Ｉ）：０．０１〜１０重量％、並びに、銀：金属量として０．００１〜１重量％を含有する、上記項１に記載の青紫光遮断ガラス。
３． ＳｉＯ２：２０〜８５重量％、Ｂ２Ｏ３：２〜７５重量％、Ａｌ２Ｏ３：１０重量％以下、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種：２〜３０重量％、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種：１〜１５重量％、ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種：１０重量％以下、Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種：５重量％以下、ＳｎＯ２：５重量％以下、ＣｕＢｒ：０．００５〜７重量％及びＣｕＩ：０．００５〜７重量％であって合計量が０．０１〜１０重量％、並びに、銀：金属量として０．００１〜１重量％を含有する、上記項１に記載の青紫光遮断ガラス。
４． ＳｉＯ２：４０〜８２重量％、Ｂ２Ｏ３：１２〜５２重量％、Ａｌ２Ｏ３：１０重量％以下、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種：２〜２０重量％、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種：１〜１５重量％、ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種：１０重量％以下、Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種：５重量％以下、ＳｎＯ２：５重量％以下、ＣｕＣｌ、ＣｕＢｒ及びＣｕＩの少なくとも１種：０．０１〜１０重量％、並びに、銀：金属量として０．０１〜１重量％を含有する、上記項１に記載の青紫光遮断ガラス。
５． ＳｉＯ２：４０〜８２重量％、Ｂ２Ｏ３：１２〜５２重量％、Ａｌ２Ｏ３：１０重量％以下、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種：２〜２０重量％、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種：１〜１５重量％、ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種：１０重量％以下、Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種：５重量％以下、ＳｎＯ２：５重量％以下、ＣｕＢｒ：０．００５〜７重量％及びＣｕＩ：０．００５〜７重量％であって合計量が０．０１〜１０重量％、並びに、銀：金属量として０．０１〜１重量％を含有する、上記項１に記載の青紫光遮断ガラス。
６． １）ＳｉＯ２、２）Ｂ２Ｏ３、３）Ａｌ２Ｏ３、４）Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種、５）ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種、６）ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種、７）Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種、８）ＳｎＯ２、並びに、９）ハロゲン化銅（Ｉ）を含有するガラス基板に、銀イオンを拡散させることにより、ガラス基板中に銀イオン及び銀化合物の少なくとも一種を形成させることにより得られる、上記項２に記載の青紫光遮断ガラス。
７． １）ＳｉＯ２、２）Ｂ２Ｏ３、３）Ａｌ２Ｏ３、４）Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種、５）ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種、６）ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種、７）Ｓｂ２Ｏ３及びＡｓ２Ｏ３少なくとも一種、８）ＳｎＯ２、並びに、９）ＣｕＢｒ及びＣｕＩを含有するガラス基板に、銀イオンを拡散させることにより、ガラス基板中に銀イオン及び銀化合物の少なくとも一種を形成させることにより得られる、上記項３に記載の青紫光遮断ガラス。
８． １）ＳｉＯ２、２）Ｂ２Ｏ３、３）Ａｌ２Ｏ３、４）Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種、５）ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種、６）ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種、７）Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種、８）ＳｎＯ２、９）Ｃｌ、Ｂｒ及びＩの少なくとも一種、並びに、１０）銀：金属量として０．０１〜１重量％を含有するガラス基板に銅イオンを拡散させることにより、ガラス基板中にＣｕＣｌ、ＣｕＢｒ及びＣｕＩの少なくとも一種のハロゲン化銅（Ｉ）を形成させることにより得られる、上記項４に記載の青紫光遮断ガラス。
９． １）ＳｉＯ２、２）Ｂ２Ｏ３、３）Ａｌ２Ｏ３、４）Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種、５）ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種、６）ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種、７）Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種、７）ＳｎＯ２、８）Ｂｒ及びＩ、並びに、９）銀：金属量として０．０１〜１重量％を含有するガラス基板に、銅イオンを拡散させることにより、ガラス基板中にＣｕＢｒ及びＣｕＩを形成することにより得られる、上記項５に記載の青紫光遮断ガラス。
１０． １）ＳｉＯ２、２）Ｂ２Ｏ３、３）Ａｌ２Ｏ３、４）Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種、５）ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種、６）ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種、７）Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種、８）ＳｎＯ２、並びに、９）Ｃｌ、Ｂｒ及びＩの少なくとも一種を含有するガラス基板に銀イオン及び銅イオンを拡散させることにより、ガラス基板中に銀イオン及び銀化合物の少なくとも一種、並びに、ＣｕＣｌ、ＣｕＢｒ及びＣｕＩの少なくとも一種のハロゲン化銅（Ｉ）を形成させることにより得られる、上記項４に記載の青紫光遮断ガラス。
１１． １）ＳｉＯ２、２）Ｂ２Ｏ３、３）Ａｌ２Ｏ３、４）Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種、５）ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種、６）ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種、７）Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種、７）ＳｎＯ２、並びに、８）Ｂｒ及びＩを含有するガラス基板に、銀イオン及び銅イオンを拡散させることにより、ガラス基板中に銀イオン及び銀化合物の少なくとも一種、並びに、ＣｕＣｌ、ＣｕＢｒ及びＣｕＩの少なくとも一種のハロゲン化銅（Ｉ）を形成させることにより得られる、上記項５に記載の青紫光遮断ガラス。
１２． 厚さ１ｍｍのガラス板に波長３００〜６００ｎｍの光を入射して透過率を測定した際に、波長４５０〜６００ｎｍの平均透過率が８５％以上であり、透過率５０％の値が波長４３２ｎｍ以上に示される、上記項１に記載の青紫光遮断ガラス。
１３． 液晶表示板保護用ガラス材である、上記項１に記載の青紫光遮断ガラス。
１４． 窓用ガラス材である、上記項１に記載の青紫光遮断ガラス。
１５． 光学用フィルター材、照明用フィルター材及びレンズ材の少なくとも一種である、上記項１に記載の青紫光遮断ガラス。
１６． 眼鏡用ガラス材である、上記項１に記載の青紫光遮断ガラス。
１７． 粉末状の紫外線吸収用配合材料である、上記項１に記載の青紫光遮断ガラス。That is, the present invention relates to the following blue-violet light blocking glass.
1. A blue-violet light-blocking glass containing copper (I) halide and silver.
2. SiO 2 : 20 to 85% by weight, B 2 O 3 : 2 to 75% by weight, Al 2 O 3 : 10% by weight or less, Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O At least one type: 2 to 30% by weight, at least one type of MgO, CaO, SrO, BaO and ZnO: 1 to 15% by weight, PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 At least one of O 3 and Gd 2 O 3 : 10 wt% or less, at least one of Sb 2 O 3 and As 2 O 3 : 5 wt% or less, SnO 2 : 5 wt% or less, copper (I) halide: 0 The blue-violet light-blocking glass according to Item 1, containing 0.001 to 10% by weight and silver: metal amount of 0.001 to 1% by weight.
3. SiO 2 : 20 to 85% by weight, B 2 O 3 : 2 to 75% by weight, Al 2 O 3 : 10% by weight or less, Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O At least one type: 2 to 30% by weight, at least one type of MgO, CaO, SrO, BaO and ZnO: 1 to 15% by weight, PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 At least one of O 3 and Gd 2 O 3 : 10 wt% or less, at least one of Sb 2 O 3 and As 2 O 3 : 5 wt% or less, SnO 2 : 5 wt% or less, CuBr: 0.005 to 7 wt % And CuI: 0.005 to 7 wt%, the total amount is 0.01 to 10 wt%, and silver: 0.001 to 1 wt% as a metal amount Purple light blocking glass.
4). SiO 2 : 40 to 82% by weight, B 2 O 3 : 12 to 52% by weight, Al 2 O 3 : 10% by weight or less, Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O At least one type: 2 to 20% by weight, at least one type of MgO, CaO, SrO, BaO and ZnO: 1 to 15% by weight, PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 At least one of O 3 and Gd 2 O 3 : 10 wt% or less, at least one of Sb 2 O 3 and As 2 O 3 : 5 wt% or less, SnO 2 : 5 wt% or less, at least one of CuCl, CuBr and CuI The blue-violet light shielding glass according to Item 1, which contains 0.01 to 10% by weight of seed and 0.01 to 1% by weight of silver: metal.
5. SiO 2 : 40 to 82% by weight, B 2 O 3 : 12 to 52% by weight, Al 2 O 3 : 10% by weight or less, Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O At least one type: 2 to 20% by weight, at least one type of MgO, CaO, SrO, BaO and ZnO: 1 to 15% by weight, PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 At least one of O 3 and Gd 2 O 3 : 10 wt% or less, at least one of Sb 2 O 3 and As 2 O 3 : 5 wt% or less, SnO 2 : 5 wt% or less, CuBr: 0.005 to 7 wt % And CuI: 0.005 to 7% by weight, and the total amount is 0.01 to 10% by weight, and silver: 0.01 to 1% by weight as the amount of metal. Purple light blocking glass.
6). 1) SiO 2, 2) B 2 O 3, 3) Al 2 O 3, 4) at least one Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O, 5) MgO, CaO, At least one of SrO, BaO and ZnO, 6) at least one of PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 O 3 and Gd 2 O 3 , 7) Sb 2 O 3 And at least one of As 2 O 3 , 8) SnO 2 , and 9) By diffusing silver ions into a glass substrate containing copper (I) halide, at least silver ions and silver compounds are contained in the glass substrate. The blue-violet light blocking glass according to Item 2, obtained by forming one kind.
7). 1) SiO 2, 2) B 2 O 3, 3) Al 2 O 3, 4) at least one Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O, 5) MgO, CaO, At least one of SrO, BaO and ZnO, 6) at least one of PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 O 3 and Gd 2 O 3 , 7) Sb 2 O 3 And at least one of As 2 O 3 , 8) SnO 2 , and 9) At least one of silver ions and a silver compound is formed in the glass substrate by diffusing silver ions in the glass substrate containing CuBr and CuI. Item 4. The blue-violet light-shielding glass according to item 3 above.
8). 1) SiO 2, 2) B 2 O 3, 3) Al 2 O 3, 4) at least one Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O, 5) MgO, CaO, At least one of SrO, BaO and ZnO, 6) at least one of PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 O 3 and Gd 2 O 3 , 7) Sb 2 O 3 And at least one of As 2 O 3 , 8) SnO 2 , 9) at least one of Cl, Br, and I, and 10) silver: copper ions are added to a glass substrate containing 0.01 to 1% by weight of metal. Item 5. The blue-violet light blocking glass according to Item 4, obtained by diffusing to form at least one kind of copper (I) halide of CuCl, CuBr and CuI in the glass substrate.
9. 1) SiO 2, 2) B 2 O 3, 3) Al 2 O 3, 4) at least one Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O, 5) MgO, CaO, At least one of SrO, BaO and ZnO, 6) at least one of PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 O 3 and Gd 2 O 3 , 7) Sb 2 O 3 And at least one of As 2 O 3 , 7) SnO 2 , 8) Br and I, and 9) Silver: by diffusing copper ions into a glass substrate containing 0.01 to 1% by weight of metal. The blue-violet light blocking glass according to Item 5, obtained by forming CuBr and CuI in a glass substrate.
10. 1) SiO 2, 2) B 2 O 3, 3) Al 2 O 3, 4) at least one Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O, 5) MgO, CaO, At least one of SrO, BaO and ZnO, 6) at least one of PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 O 3 and Gd 2 O 3 , 7) Sb 2 O 3 And by diffusing silver ions and copper ions into a glass substrate containing at least one of As 2 O 3 , 8) SnO 2 , and 9) at least one of Cl, Br, and I. Item 5. The blue-violet light blocking glass according to item 4, obtained by forming at least one silver compound and at least one copper (I) halide of CuCl, CuBr and CuI.
11. 1) SiO 2, 2) B 2 O 3, 3) Al 2 O 3, 4) at least one Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O, 5) MgO, CaO, At least one of SrO, BaO and ZnO, 6) at least one of PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 O 3 and Gd 2 O 3 , 7) Sb 2 O 3 And at least one of As 2 O 3 , 7) SnO 2 , and 8) By diffusing silver ions and copper ions into a glass substrate containing Br and I, at least silver ions and silver compounds in the glass substrate are diffused. 6. The blue-violet light-shielding glass according to item 5, obtained by forming one kind and at least one kind of copper (I) halide of CuCl, CuBr and CuI.
12 When light having a wavelength of 300 to 600 nm is incident on a glass plate having a thickness of 1 mm and the transmittance is measured, the average transmittance at a wavelength of 450 to 600 nm is 85% or more, and the value of the transmittance 50% is a wavelength of 432 nm or more. The blue-violet light blocking glass according to Item 1, which is shown in (1).
13. The blue-violet light blocking glass according to Item 1, which is a glass material for protecting a liquid crystal display panel.
14 The blue-violet light blocking glass according to Item 1, which is a glass material for windows.
15. The blue-violet light blocking glass according to Item 1, which is at least one of an optical filter material, an illumination filter material, and a lens material.
16. 2. The blue-violet light blocking glass according to item 1, which is a glass material for spectacles.
17. Item 2. The blue-violet light blocking glass according to Item 1, which is a powdery ultraviolet absorbing compounding material.
以下、本発明の青紫光遮断ガラスについて詳細に説明する。 Hereinafter, the blue-violet light blocking glass of the present invention will be described in detail.
青紫光遮断ガラス
本発明の青紫光遮断ガラスは、ハロゲン化銅（Ｉ）微粒子を含有し、吸収型の遮断能を発揮する青紫光遮断ガラスであって、ハロゲン化銅（Ｉ）微粒子に加えて銀を含むことを特徴とする。Blue-violet light-blocking glass The blue-violet light-blocking glass of the present invention is a blue-violet light-blocking glass that contains copper (I) halide fine particles and exhibits absorption-type blocking ability. It contains silver.
本発明の青紫光遮断ガラスは、ハロゲン化銅（Ｉ）微粒子に加えて銀を含有するため、波長４５０〜６００ｎｍの光を十分に透過し、４５０ｎｍよりも短波長の光をシャープに遮断できる。具体的には、好適な実施態様では、厚さ１ｍｍのガラス板に波長３００〜６００ｎｍの光を（ガラス板の板面に対して垂直方向から）入射して透過率を測定した際に、４５０〜６００ｎｍの光の平均透過率が８５％以上であり、透過率５０％の値が波長４３２ｎｍ以上に示される。即ち、本発明の青紫光遮断ガラスは、４５０〜６００ｎｍの透過率が高く、且つ、従来品に比して４５０ｎｍ付近でシャープな遮断機能（波長傾斜幅：Δλが小さい）を有する。なお、本明細書におけるΔλは、ＪＩＳ Ｂ ７１１３によって規定される波長傾斜幅である。 Since the blue-violet light blocking glass of the present invention contains silver in addition to the copper (I) halide fine particles, it can sufficiently transmit light having a wavelength of 450 to 600 nm and sharply block light having a wavelength shorter than 450 nm. Specifically, in a preferred embodiment, when light having a wavelength of 300 to 600 nm is incident on a glass plate having a thickness of 1 mm (from a direction perpendicular to the plate surface of the glass plate) and the transmittance is measured, 450 The average transmittance of light at ˜600 nm is 85% or more, and a value of 50% transmittance is shown at a wavelength of 432 nm or more. That is, the blue-violet light blocking glass of the present invention has a high transmittance of 450 to 600 nm and a sharp blocking function (wavelength gradient width: Δλ is small) near 450 nm as compared with the conventional product. In this specification, Δλ is a wavelength inclination width defined by JIS B 7113.
また、本発明の青紫光遮断ガラスはＣｄ化合物を用いる必要がないため、安全性が高く、製造及び廃棄処理が容易である。 Further, since the blue-violet light blocking glass of the present invention does not require the use of a Cd compound, it is highly safe and easy to manufacture and dispose of.
本発明の青紫光遮断ガラスは、ハロゲン化銅（Ｉ）及び銀以外の成分は限定的ではなく、従来からガラスに用いられている各種成分を含有できる。例えば、ＳｉＯ２、Ｂ２Ｏ３、Ａｌ２Ｏ３、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ、Ｃｓ２Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３、Ｇｄ２Ｏ３、Ｓｂ２Ｏ３、Ａｓ２Ｏ３、ＳｎＯ２等の中から選択した成分を含有する。The blue-violet light blocking glass of the present invention is not limited to components other than copper (I) halide and silver, and can contain various components conventionally used in glass. For example, SiO 2, B 2 O 3 , Al 2 O 3, Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O, MgO, CaO, SrO, BaO, ZnO, PbO, Nb 2 O 5. A component selected from ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 O 3 , Gd 2 O 3 , Sb 2 O 3 , As 2 O 3 , SnO 2 and the like is contained.
本発明の青紫光遮断ガラスの好適な組成としては、例えば、以下が例示される。 Examples of the preferred composition of the blue-violet light blocking glass of the present invention include the following.
≪組成１≫
ＳｉＯ２：２０〜８５重量％、Ｂ２Ｏ３：２〜７５重量％、Ａｌ２Ｏ３：１０重量％以下、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種：２〜３０重量％、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種：１〜１５重量％、ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種：１０重量％以下、Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種：５重量％以下、ＳｎＯ２：５重量％以下、ハロゲン化銅（Ｉ）：０．０１〜１０重量％、並びに、銀：金属量として０．００１〜１重量％を含有する青紫光遮断ガラス。なお、上記Ｓｉ〜Ｓｎまでの金属については、酸化物組成で示している（以下同様）。≪Composition 1≫
SiO 2 : 20 to 85% by weight, B 2 O 3 : 2 to 75% by weight, Al 2 O 3 : 10% by weight or less, Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O At least one type: 2 to 30% by weight, at least one type of MgO, CaO, SrO, BaO and ZnO: 1 to 15% by weight, PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 At least one of O 3 and Gd 2 O 3 : 10 wt% or less, at least one of Sb 2 O 3 and As 2 O 3 : 5 wt% or less, SnO 2 : 5 wt% or less, copper (I) halide: 0 Blue-violet light shielding glass containing 0.001 to 10% by weight and 0.001 to 1% by weight of silver: metal. In addition, about the said metal to Si-Sn, it has shown by the oxide composition (hereinafter the same).
≪組成２≫
ＳｉＯ２：２０〜８５重量％、Ｂ２Ｏ３：２〜７５重量％、Ａｌ２Ｏ３：１０重量％以下、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種：２〜３０重量％、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種：１〜１５重量％、ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種：１０重量％以下、Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種：５重量％以下、ＳｎＯ２：５重量％以下、ＣｕＢｒ：０．００５〜７重量％及びＣｕＩ：０．００５〜７重量％であって合計量が０．０１〜１０重量％、並びに、銀：金属量として０．００１〜１重量％を含有する青紫光遮断ガラス。<< Composition 2 >>
SiO 2 : 20 to 85% by weight, B 2 O 3 : 2 to 75% by weight, Al 2 O 3 : 10% by weight or less, Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O At least one type: 2 to 30% by weight, at least one type of MgO, CaO, SrO, BaO and ZnO: 1 to 15% by weight, PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 At least one of O 3 and Gd 2 O 3 : 10 wt% or less, at least one of Sb 2 O 3 and As 2 O 3 : 5 wt% or less, SnO 2 : 5 wt% or less, CuBr: 0.005 to 7 wt % And CuI: 0.005 to 7% by weight, a total amount of 0.01 to 10% by weight, and silver: a blue-violet light shielding glass containing 0.001 to 1% by weight as a metal amount.
≪組成３：組成１の好ましい組成≫
ＳｉＯ２：４０〜８２重量％、Ｂ２Ｏ３：１２〜５２重量％、Ａｌ２Ｏ３：１０重量％以下、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種：２〜２０重量％、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種：１〜１５重量％、ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種：１０重量％以下、Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種：５重量％以下、ＳｎＯ２：５重量％以下、ＣｕＣｌ、ＣｕＢｒ及びＣｕＩの少なくとも１種：０．０１〜１０重量％、並びに、銀：金属量として０．０１〜１重量％を含有する青紫光遮断ガラス。<< Composition 3: Preferred composition of composition 1 >>
SiO 2 : 40 to 82% by weight, B 2 O 3 : 12 to 52% by weight, Al 2 O 3 : 10% by weight or less, Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O At least one type: 2 to 20% by weight, at least one type of MgO, CaO, SrO, BaO and ZnO: 1 to 15% by weight, PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 At least one of O 3 and Gd 2 O 3 : 10 wt% or less, at least one of Sb 2 O 3 and As 2 O 3 : 5 wt% or less, SnO 2 : 5 wt% or less, at least one of CuCl, CuBr and CuI Species: Blue-violet light shielding glass containing 0.01 to 10% by weight and silver: 0.01 to 1% by weight as a metal amount.
≪組成４：組成２の好ましい組成≫
ＳｉＯ２：４０〜８２重量％、Ｂ２Ｏ３：１２〜５２重量％、Ａｌ２Ｏ３：１０重量％以下、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏの少なくとも一種：２〜２０重量％、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの少なくとも一種：１〜１５重量％、ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３の少なくとも一種：１０重量％以下、Ｓｂ２Ｏ３及びＡｓ２Ｏ３の少なくとも一種：５重量％以下、ＳｎＯ２：５重量％以下、ＣｕＢｒ：０．００５〜７重量％及びＣｕＩ：０．００５〜７重量％であって合計量が０．０１〜１０重量％、並びに、銀：金属量として０．０１〜１重量％を含有する青紫光遮断ガラス。<< Composition 4: Preferred composition of composition 2 >>
SiO 2 : 40 to 82% by weight, B 2 O 3 : 12 to 52% by weight, Al 2 O 3 : 10% by weight or less, Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O At least one type: 2 to 20% by weight, at least one type of MgO, CaO, SrO, BaO and ZnO: 1 to 15% by weight, PbO, Nb 2 O 5, ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 At least one of O 3 and Gd 2 O 3 : 10 wt% or less, at least one of Sb 2 O 3 and As 2 O 3 : 5 wt% or less, SnO 2 : 5 wt% or less, CuBr: 0.005 to 7 wt % And CuI: 0.005 to 7% by weight, a total amount of 0.01 to 10% by weight, and silver: a blue-violet light blocking glass containing 0.01 to 1% by weight as a metal amount.
多成分系ガラス材料においては、各成分が相互に影響して、ガラス材料の固有の特性を決定するため、各成分の量的範囲を各成分の特性に応じて論じることは必ずしも妥当ではないが、以下に、上記好適組成において各成分の量的範囲を規定した根拠を述べる。 In multicomponent glass materials, each component influences each other to determine the specific properties of the glass material, so it is not always appropriate to discuss the quantitative range of each component according to the properties of each component. Hereinafter, the grounds for defining the quantitative ranges of the respective components in the preferred composition will be described.
ＳｉＯ２は、ガラス網目を構成する主成分である。ＳｉＯ２の含有量は、２０〜８５重量％程度が好ましく、４０〜８２重量％程度がより好ましい。ＳｉＯ２の含有量が８５重量％を上回るとガラスの溶融性が悪化するおそれがある。ＳｉＯ２の含有量が２０重量％を下回ると化学的耐久性が不充分で変色の原因となるおそれがある。SiO 2 is a main component constituting the glass network. The content of SiO 2 is preferably about 20 to 85% by weight, and more preferably about 40 to 82% by weight. If the SiO 2 content exceeds 85% by weight, the meltability of the glass may be deteriorated. If the content of SiO 2 is less than 20% by weight, the chemical durability is insufficient and there is a risk of causing discoloration.
Ｂ２Ｏ３は、ガラスの溶融性を向上させる成分である。また特定組成ではガラス網目を構成する成分ともなる。Ｂ２Ｏ３の含有量は、２〜７５重量％程度が好ましく、１２〜５２重量％程度がより好ましい。Ｂ２Ｏ３の含有量が７５重量％を上回るとガラスの化学的耐久性が不十分となるおそれがある。Ｂ２Ｏ３の含有量が２重量％を下回ると光透過特性及びガラスの溶融性が悪化するおそれがある。B 2 O 3 is a component that improves the meltability of the glass. Moreover, it becomes a component which comprises a glass network with a specific composition. The content of B 2 O 3 is preferably about 2 to 75% by weight, and more preferably about 12 to 52% by weight. If the content of B 2 O 3 exceeds 75% by weight, the chemical durability of the glass may be insufficient. If the content of B 2 O 3 is less than 2% by weight, the light transmission characteristics and the glass melting property may be deteriorated.
Ａｌ２Ｏ３は、ガラスの失透を抑制し、化学的耐久性を高める成分である。Ａｌ２Ｏ３の含有量は、１０重量％以下が好ましい。下限値は限定的ではないが、所定の効果を得るためには１重量％以上とする。Ａｌ２Ｏ３の含有量が１０重量％を上回るとガラス溶融性が低下するおそれがある。Al 2 O 3 is a component that suppresses devitrification of glass and enhances chemical durability. The content of Al 2 O 3 is preferably 10% by weight or less. The lower limit is not limited, but is 1% by weight or more in order to obtain a predetermined effect. If the content of Al 2 O 3 exceeds 10% by weight, the glass meltability may be lowered.
Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２Ｏ及びＣｓ２Ｏは、ガラスの溶融性を向上させる成分である。これらの成分は、一種又は二種以上で使用できる。これらの含有量は、合計量で２〜３０重量％程度が好ましく、２〜２０重量％程度がより好ましい。これらの含有量が３０重量％を上回るとガラスの化学的耐久性が不十分となるおそれがある。これらの含有量が２重量％を下回るとガラスの溶融性が不十分となるおそれがある。Li 2 O, Na 2 O, K 2 O, Rb 2 O, and Cs 2 O are components that improve the meltability of the glass. These components can be used alone or in combination of two or more. The total content is preferably about 2 to 30% by weight, more preferably about 2 to 20% by weight. If these contents exceed 30% by weight, the chemical durability of the glass may be insufficient. If these contents are less than 2% by weight, the meltability of the glass may be insufficient.
ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯは、ガラスの化学的耐久性を向上させる成分である。これらの成分は、一種又は二種以上で使用できる。これらの含有量は、合計量で１〜１５重量％程度が好ましく、１〜１０重量％程度がより好ましい。これらの含有量が１５重量％を上回るとガラスの溶融性が低下するおそれがある。これらの含有量が１重量％を下回るとガラスの化学的耐久性が不十分となるおそれがある。 MgO, CaO, SrO, BaO and ZnO are components that improve the chemical durability of the glass. These components can be used alone or in combination of two or more. The total content is preferably about 1 to 15% by weight, and more preferably about 1 to 10% by weight. If these contents exceed 15% by weight, the meltability of the glass may be lowered. If these contents are less than 1% by weight, the chemical durability of the glass may be insufficient.
ＰｂＯ、Ｎｂ２Ｏ５、ＺｒＯ２、Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ３及びＧｄ２Ｏ３は、ガラスの化学的耐久性を向上させる成分である。これらの成分は一種又は二種以上で使用できる。これらの含有量は、合計量で１０重量％以下が好ましい。下限値は限定的ではないが、所定の効果を得るためには１重量％以上とする。これらの含有量が１０重量％を上回るとガラスの溶融性が悪くなるおそれがある。PbO, Nb 2 O 5 , ZrO 2 , La 2 O 3 , Y 2 O 3 , Ta 2 O 3 and Gd 2 O 3 are components that improve the chemical durability of the glass. These components can be used alone or in combination of two or more. These contents are preferably 10% by weight or less in total. The lower limit is not limited, but is 1% by weight or more in order to obtain a predetermined effect. If these contents exceed 10% by weight, the meltability of the glass may be deteriorated.
Ｓｂ２Ｏ３及びＡｓ２Ｏ３は、ガラスの清澄剤として作用する。これらの成分は、一種又は二種以上で使用できる。これらの含有量は、合計量で５重量％以下が好ましい。下限値は限定的ではないが、所定の効果を得るためには０．０５重量％以上とする。これらの含有量が５重量％を上回るとガラスの溶融性が悪くなるおそれがある。Sb 2 O 3 and As 2 O 3 act as glass fining agents. These components can be used alone or in combination of two or more. These contents are preferably 5% by weight or less in total. The lower limit is not limited, but is 0.05% by weight or more in order to obtain a predetermined effect. If these contents exceed 5% by weight, the meltability of the glass may be deteriorated.
ＳｎＯ２の含有量は、５重量％以下が好ましい。Ｓｎは、Ａｌ、Ｚｎ等の金属又はショ糖、尿素等の有機物などと同様に、ガラス溶融時において還元剤として作用する。即ち、Ｓｎは、ガラス溶融時に銅成分を１価（Ｃｕ＋）に還元する作用がある。ＳｎＯ２の含有量の下限値は限定的ではないが、所定の効果を得るためには０．０２重量％以上とする。他方、ＳｎＯ２の含有量が５重量％を上回るとガラス中に銅が析出するおそれがあり好ましくない。The content of SnO 2 is preferably 5% by weight or less. Sn acts as a reducing agent at the time of glass melting, like metals such as Al and Zn, or organic substances such as sucrose and urea. That is, Sn has the effect | action which reduces a copper component to monovalence (Cu <+> ) at the time of glass melting. The lower limit of the content of SnO 2 is not limited, but is 0.02% by weight or more in order to obtain a predetermined effect. On the other hand, if the SnO 2 content exceeds 5% by weight, copper may be precipitated in the glass, which is not preferable.
ハロゲン化銅（Ｉ）としては限定的ではないが、例えば、ＣｕＣｌ、ＣｕＢｒ、ＣｕＩ等が挙げられる。これらのハロゲン化銅（Ｉ）は、一種又は二種以上で使用できる。ハロゲン化銅は、紫外線又は可視域の任意波長の光を吸収する着色剤として作用する。ハロゲン化銅（Ｉ）の含有量は、合計量で０．０１〜１０重量％程度が好ましく、０．３〜８重量％程度がより好ましい。ハロゲン化銅（Ｉ）を２種以上含有する場合には、ＣｕＢｒとＣｕＩとを組み合わせて用いることが好ましく、より具体的には、ＣｕＢｒを０．００５〜７重量％含有し、ＣｕＩを０．００５〜７重量％含有し、合計量が０．０１〜１０重量％であることが好ましい。 The copper (I) halide is not limited, and examples thereof include CuCl, CuBr, and CuI. These copper (I) halides can be used alone or in combination. Copper halide acts as a colorant that absorbs light of any wavelength in the ultraviolet or visible range. The total content of copper (I) halide is preferably about 0.01 to 10% by weight, and more preferably about 0.3 to 8% by weight. When two or more types of copper (I) halides are contained, it is preferable to use a combination of CuBr and CuI. More specifically, CuBr is contained in an amount of 0.005 to 7% by weight, and CuI is 0.1%. It is preferable to contain 005-7 weight% and the total amount is 0.01-10 weight%.
ガラス中のハロゲン化銅（Ｉ）の含有量を上記範囲に制御することにより、波長４２０ｎｍ以下の任意の光をほぼ完全に遮断し、それより長波長の光をほぼ完全に透過し、更に波長傾斜幅（Δλ）の小さいシャープな吸収特性が得られる。ハロゲン化銅の含有量が０．０１重量％を下回ると所望の効果が得られ難くなる。ハロゲン化銅の含有量が１０重量％を上回るとガラスが失透し易くなるおそれがある。 By controlling the content of copper (I) halide in the glass within the above range, any light with a wavelength of 420 nm or less is almost completely blocked, and light having a longer wavelength is almost completely transmitted. A sharp absorption characteristic having a small inclination width (Δλ) can be obtained. If the content of copper halide is less than 0.01% by weight, it is difficult to obtain a desired effect. If the content of copper halide exceeds 10% by weight, the glass tends to be devitrified.
上記ハロゲン化銅（Ｉ）は、ガラス中に結晶微粒子の状態で含有される。結晶微粒子の大きさは限定的ではないが、平均粒子径は０．１〜１０ｎｍ程度である。 The copper (I) halide is contained in the form of crystal fine particles in the glass. The size of the crystal fine particles is not limited, but the average particle size is about 0.1 to 10 nm.
本発明の青紫光遮断ガラスは、上記成分以外に銀を含有する。銀を含有することにより、遮断する光の波長を長波長側にシフトすることができる。即ち、４５０〜６００ｎｍの高透過率を維持しながら、より４５０ｎｍ近傍において４５０ｎｍ未満の光を遮断できる。 The blue-violet light blocking glass of the present invention contains silver in addition to the above components. By containing silver, the wavelength of light to be blocked can be shifted to the long wavelength side. That is, while maintaining a high transmittance of 450 to 600 nm, light of less than 450 nm can be blocked near 450 nm.
銀の含有量としては、金属量として０．００１〜１重量％程度が好ましく、０．０１〜１重量％程度がより好ましく、０．０３〜０．０８重量％程度が更に好ましい。銀の含有量が０．００１重量％を下回ると所望の効果が得られ難くなる。銀の含有量が１重量％を上回る場合にはガラス中に銀が析出するおそれがある。 The silver content is preferably about 0.001 to 1% by weight, more preferably about 0.01 to 1% by weight, and still more preferably about 0.03 to 0.08% by weight as the metal amount. When the silver content is less than 0.001% by weight, it is difficult to obtain a desired effect. If the silver content exceeds 1% by weight, silver may be precipitated in the glass.
銀は、ガラス中において、銀イオン、銀微粒子及びハロゲン化銀微粒子の少なくとも一種の状態で含有される。微粒子（結晶微粒子を含む）の大きさは限定的ではないが、平均粒子径は０．１〜１０ｎｍ程度である。 Silver is contained in the glass in at least one state of silver ions, silver fine particles, and silver halide fine particles. The size of the fine particles (including crystal fine particles) is not limited, but the average particle size is about 0.1 to 10 nm.
本発明の青紫光遮断ガラスの用途は限定的ではないが、例えば、下記が挙げられる。 The use of the blue-violet light blocking glass of the present invention is not limited, but examples thereof include the following.
（１）液晶表示板保護用ガラス材
液晶表示板のバックライトからは、可視光線とともに紫外線も照射されるが、照射光を視認する者の目の保護及び液晶の劣化を考慮すると、紫外線を除去するのが好ましい。(1) Glass material for protecting liquid crystal display panel The backlight of the liquid crystal display panel is irradiated with ultraviolet rays as well as visible light. However, considering the protection of the eyes of those who see the irradiated light and the deterioration of the liquid crystals, the ultraviolet rays are removed. It is preferable to do this.
本発明の青紫光遮断ガラスは、液晶表示板保護用ガラス材として有用である。即ち、当該ガラスからなる保護板を液晶表示板の前面又は背面に設置することにより、バックライトから照射される紫外線を選択的且つシャープに遮断できる。具体的には、液晶表示板の背面に設置する場合には、バックライトの光から紫外線を除去して液晶に照射するため、液晶の劣化を防止できるとともに、視認者の目も保護できる。他方、液晶表示板の前面に設置する場合には、視認者の目の保護に寄与する。 The blue-violet light blocking glass of the present invention is useful as a glass material for protecting a liquid crystal display panel. That is, by installing the protective plate made of the glass on the front surface or the back surface of the liquid crystal display plate, it is possible to selectively and sharply block ultraviolet rays irradiated from the backlight. Specifically, when it is installed on the back side of the liquid crystal display panel, ultraviolet rays are removed from the light of the backlight and the liquid crystal is irradiated, so that the deterioration of the liquid crystal can be prevented and the eyes of the viewer can be protected. On the other hand, when it is installed on the front surface of the liquid crystal display panel, it contributes to protecting the eyes of the viewer.
（２）窓用ガラス材
美術工芸品店、高級衣料品店の外装ガラス、各種研究室の窓ガラス、自動車の窓ガラス等には、従来、フロートガラスが使用されている。しかしながら、当該フロートガラスは、太陽光に含まれる紫外線を遮断することが困難である。そのため、美術工芸品の褪色及び劣化、衣料品の変色及び劣化、各種研究への悪影響、自動車内装品の変質及び劣化等の問題がある。また、自動車の乗員にとっては、紫外線による目の障害、日焼け等の皮膚障害発生の問題がある。(2) Glass materials for windows Float glass is conventionally used for exterior glass of art craft shops, luxury clothing stores, window glass of various laboratories, window glass of automobiles, and the like. However, it is difficult for the float glass to block ultraviolet rays contained in sunlight. Therefore, there are problems such as discoloration and deterioration of arts and crafts, discoloration and deterioration of clothing, adverse effects on various researches, alteration and deterioration of automobile interior goods. In addition, automobile passengers have problems such as eye damage caused by ultraviolet rays and skin damage such as sunburn.
本発明の青紫光遮断ガラスは、窓用ガラス材として有用である。即ち、当該ガラスから外装ガラス及び窓ガラスを形成することにより、太陽光に含まれる紫外線を選択的且つシャープに遮断し、可視光を選択的に透過できる。これにより、上記問題点を解消又は軽減できる。 The blue-violet light blocking glass of the present invention is useful as a glass material for windows. That is, by forming exterior glass and window glass from the glass, ultraviolet rays contained in sunlight can be selectively and sharply blocked, and visible light can be selectively transmitted. Thereby, the said problem can be eliminated or reduced.
（３）光学用フィルター材、照明用フィルター材及びレンズ材
カメラなどの光学機器類においては、従来、光学用フィルター、照明用フィルター、レンズ材が用いられている。これらの部材は、紫外線の遮断効率を高めることにより、更に鮮明な画像等を得ることができる。(3) Optical filter material, illumination filter material, and lens material In optical devices such as cameras, optical filters, illumination filters, and lens materials are conventionally used. These members can obtain a clearer image or the like by increasing the ultraviolet blocking efficiency.
本発明の青紫光遮断ガラスは、紫外線を選択的且つシャープに遮断できるため、鮮明な画像等を得るために有利な光学用フィルター材、照明用フィルター及びレンズ材として使用できる。 Since the blue-violet light blocking glass of the present invention can selectively and sharply block ultraviolet rays, it can be used as an optical filter material, an illumination filter, and a lens material that are advantageous for obtaining clear images and the like.
（４）眼鏡用ガラス材
眼鏡用ガラスは、眼鏡使用者の保護の観点からは、太陽光及び各種照射光に含まれる紫外線をシャープに遮断できることが望ましい。(4) Glasses for glasses It is desirable that glasses for glasses can sharply block ultraviolet rays contained in sunlight and various types of irradiation light from the viewpoint of protection for spectacle users.
本発明の青紫光遮断ガラスは、紫外線を選択的且つシャープに遮断できることにより、眼鏡用ガラス材として有用である。 The blue-violet light blocking glass of the present invention is useful as a glass material for glasses because it can selectively and sharply block ultraviolet rays.
（５）粉末状の紫外線吸収用配合材料
本発明の青紫光遮断ガラスは、紫外線を選択的且つシャープに遮断できることにより、粉末の状態で紫外線吸収剤として使用できる。紫外線吸収剤は他のものを組み合わせて使用することもできる。粉末の平均粒子径は限定されないが、１〜１０μｍ程度が好ましい。具体的には、粉末状態で樹脂組成物、塗料組成物等に配合することにより、樹脂製品、塗膜等に紫外線吸収能を付与し、これらの耐候性、褪色性等を改善できる。(5) Powdery UV-absorbing compounding material The blue-violet light blocking glass of the present invention can be used as an ultraviolet absorber in a powder state by selectively and sharply blocking ultraviolet rays. An ultraviolet absorber can also be used in combination with other things. Although the average particle diameter of powder is not limited, about 1-10 micrometers is preferable. Specifically, by blending with a resin composition, a coating composition or the like in a powder state, it is possible to impart ultraviolet absorbing ability to a resin product, a coating film or the like, and to improve the weather resistance, fading property and the like.
（６）紫外線硬化型樹脂の硬化設備におけるガラス材
紫外線硬化型樹脂を硬化させるためには、高圧水銀ランプ、メタルハライドランプ等の、高エネルギーの紫外線を照射する光源を用いる。かかる高エネルギー紫外線は、樹脂の硬化に不可欠ではあるが、作業者の安全性確保、設備の劣化防止等の観点からは、必要部位以外への照射は避けるべきである。(6) Glass material in curing equipment for ultraviolet curable resin In order to cure the ultraviolet curable resin, a light source that irradiates high-energy ultraviolet rays, such as a high-pressure mercury lamp and a metal halide lamp, is used. Such high-energy ultraviolet rays are indispensable for curing the resin, but from the viewpoints of ensuring the safety of workers and preventing the deterioration of the facilities, irradiation to other than necessary areas should be avoided.
本発明の青紫光遮断ガラスは、かかる硬化設備における監視窓用ガラス材として有用である。監視窓用ガラス材として用いることにより、作業者の目を確実に保護できる。また、当該ガラスを防護材として各種設備を被覆する態様で配置する場合には、設備の劣化を防止できる。 The blue-violet light blocking glass of the present invention is useful as a glass material for monitoring windows in such curing equipment. By using it as a monitoring window glass material, the eyes of the operator can be reliably protected. Moreover, when arrange | positioning in the aspect which coat | covers various facilities by using the said glass as a protective material, degradation of facilities can be prevented.
青紫光遮断ガラスの製造方法
本発明の青紫光遮断ガラスの製造方法は特に限定されず、上記所定の組成となるように原料を配合し、公知のガラス製造方法に従って処理すればよい。 Manufacturing method of blue-violet light blocking glass The manufacturing method of the blue-violet light blocking glass of the present invention is not particularly limited, and the raw materials may be blended so as to have the above-mentioned predetermined composition and processed according to a known glass manufacturing method.
ガラス中の各成分の原料（ガラス原料）としては特に限定されないが、各金属の酸化物、炭酸塩、硫酸塩、硝酸塩、水酸化物等が挙げられる。 Although it does not specifically limit as a raw material (glass raw material) of each component in glass, The oxide, carbonate, sulfate, nitrate, hydroxide, etc. of each metal are mentioned.
ハロゲン化銅（Ｉ）の原料としては、ハロゲン化銅のほかに、銅源とハロゲン源との混合物が挙げられる。銅源としては、酸化物、ハロゲン化銅等が挙げられる。ハロゲン源としては、ハロゲン化リチウム、ハロゲン化ナトリウム、ハロゲン化カリウム、ハロゲン化ルビジウム、ハロゲン化セシウム等のハロゲン化アルカリ化合物が挙げられる。 Examples of the raw material for the copper (I) halide include a mixture of a copper source and a halogen source in addition to the copper halide. Examples of the copper source include oxides and copper halides. Examples of the halogen source include alkali halide compounds such as lithium halide, sodium halide, potassium halide, rubidium halide, and cesium halide.
銀の原料としては、金属銀、酸化銀、ハロゲン化銀、硫酸銀、硝酸銀等が挙げられる。 Examples of the silver raw material include metallic silver, silver oxide, silver halide, silver sulfate, and silver nitrate.
青紫光遮断ガラスの製造に際しては、例えば、最終的に所定の組成となるように上記原料を調合し、１２００〜１５００℃程度の温度で溶融・撹拌・清澄後、型に流し込み、冷却中又は冷却後、４５０〜７００℃程度の温度で０．１〜５時間程度熱処理を行ない、切断、研磨等の加工を経る。 When producing blue-violet light-shielding glass, for example, the above raw materials are prepared so as to finally have a predetermined composition, melted, stirred and clarified at a temperature of about 1200 to 1500 ° C., and then poured into a mold, during cooling or cooling Thereafter, heat treatment is performed at a temperature of about 450 to 700 ° C. for about 0.1 to 5 hours, and processing such as cutting and polishing is performed.
溶融工程では、銅原料がＣｕ＋の状態となるように、中性又は還元雰囲気が好ましい。還元剤としては、前記Ｓｎ、Ａｌ、Ｚｎ等の金属（化合物を含む）、ショ糖、尿素等の有機物などが挙げられる。In the melting step, a neutral or reducing atmosphere is preferable so that the copper raw material is in a Cu + state. Examples of the reducing agent include metals (including compounds) such as Sn, Al, and Zn, and organic substances such as sucrose and urea.
冷却・熱処理工程では、ガラスに熱的歪みが生じないように温度条件を管理することが好ましい。冷却速度としては１０〜１００℃／ｈｒ程度が好ましく、３０〜５０℃／ｈｒ程度がより好ましい。加熱速度としては１０〜１００℃／ｈｒ程度が好ましく、３０〜７０℃／ｈｒ程度がより好ましい。かかるゆっくりとした速度で降温及び昇温させることにより、上記ハロゲン化銅の結晶微粒子の平均粒子径は制御し易くなる。 In the cooling / heat treatment step, it is preferable to control the temperature conditions so that thermal distortion does not occur in the glass. The cooling rate is preferably about 10 to 100 ° C./hr, more preferably about 30 to 50 ° C./hr. The heating rate is preferably about 10 to 100 ° C./hr, more preferably about 30 to 70 ° C./hr. By lowering and raising the temperature at such a slow rate, the average particle diameter of the copper halide crystal fine particles can be easily controlled.
その他、上記製造方法以外に、例えば、ハロゲン化銅（Ｉ）成分及び銀成分の一方又は両方を含有しないガラス基板に対して、銅イオン及び銀イオンの一方又は両方を拡散させることにより、ガラス基板中にハロゲン化銅（Ｉ）成分及び銀成分（銀イオン及び銀化合物の少なくとも一種）を形成することによっても、目的の青紫光遮断ガラスは得られる。 In addition to the above manufacturing method, for example, by diffusing one or both of copper ions and silver ions with respect to a glass substrate not containing one or both of a copper halide (I) component and a silver component, a glass substrate By forming a copper (I) halide component and a silver component (at least one of silver ions and silver compounds) therein, the desired blue-violet light blocking glass can be obtained.
上記銀イオン及び銅イオンの一方又は両方をガラス基板に拡散させる方法としては、例えば、ガラス基板の表面に銀金属又は銀化合物（及び／又は銅金属又は銅化合物）を含有する皮膜を形成した後熱処理をする方法、銀塩及び／又は銅塩の溶融槽にガラス基材を浸漬する方法等によって行うことができる。以下、主として銅イオンを拡散させる場合を例に挙げて説明する。 As a method of diffusing one or both of the silver ions and copper ions into the glass substrate, for example, after forming a film containing silver metal or silver compound (and / or copper metal or copper compound) on the surface of the glass substrate It can be performed by a method of heat treatment, a method of immersing a glass substrate in a silver salt and / or copper salt melting tank, or the like. Hereinafter, a case where copper ions are mainly diffused will be described as an example.
ガラス基材の表面に銅金属又は銅化合物を含有する皮膜を形成する方法としては、例えば、銅化合物を含有するペーストを塗布し乾燥する方法、銅アルコキシド溶液を用いるゾルゲル法によって皮膜を形成する方法、真空蒸着法、ＣＶＤ法（化学気相堆積法）、イオン蒸着法、スパッタリング法、溶射法等の方法で銅又は銅化合物の皮膜を形成する方法が挙げられる。 Examples of a method for forming a film containing copper metal or a copper compound on the surface of a glass substrate include, for example, a method of applying and drying a paste containing a copper compound, and a method of forming a film by a sol-gel method using a copper alkoxide solution. And a method of forming a film of copper or a copper compound by a method such as vacuum vapor deposition, CVD (chemical vapor deposition), ion vapor deposition, sputtering, or thermal spraying.
銅金属又は銅化合物を含有する皮膜の厚さは、形成すべき青紫光遮断ガラスの特性に応じて適宜決めればよいが、通常、０．１〜２ｍｍ程度の厚さとすればよい。 The thickness of the film containing copper metal or a copper compound may be appropriately determined according to the characteristics of the blue-violet light blocking glass to be formed, but is usually about 0.1 to 2 mm.
皮膜を形成した後の熱処理は、例えば、４００〜７００℃程度の温度であってガラス基材の屈伏点以下の温度で１０分〜２０時間程度行う。その後、水洗することによって、ガラス基材の表面にハロゲン化銅の微結晶層を形成した青紫光遮断ガラスが得られる。 The heat treatment after forming the film is performed, for example, at a temperature of about 400 to 700 ° C. and a temperature below the yield point of the glass substrate for about 10 minutes to 20 hours. Thereafter, by washing with water, a blue-violet light blocking glass in which a microcrystal layer of copper halide is formed on the surface of the glass substrate is obtained.
これらの方法の内で、銅化合物を含有するペーストを塗布し乾燥する方法について次に説明する。銅化合物を含有するペーストとしては、特に限定はなく、ガラス基材上に塗布し得る適度な粘度を有し、熱処理によりガラス基材中に銅イオンを拡散させることのできる銅化合物を含有するペーストであればよい。 Among these methods, a method of applying and drying a paste containing a copper compound will be described below. There is no limitation in particular as a paste containing a copper compound, The paste contains the copper compound which has moderate viscosity which can be apply | coated on a glass base material, and can diffuse a copper ion in a glass base material by heat processing. If it is.
銅化合物としては、例えば、ＣｕＳＯ４、ＣｕＣｌ、ＣｕＣｌ２、ＣｕＢｒ、ＣｕＢｒ２、Ｃｕ２Ｏ、ＣｕＯ、Ｃｕ（ＮＯ３）・３Ｈ２Ｏ、ＣｕＳ等が挙げられる。ペースト中の銅化合物の含有量は、特に限定されないが、通常２０〜７０重量％程度、好ましくは３０〜６０重量％程度である。ペーストには、通常バインダー成分が含まれるが、バインダー成分としては、熱処理工程において分解し、水洗により容易に除去される樹脂成分が好ましい。Examples of the copper compound include CuSO 4 , CuCl, CuCl 2 , CuBr, CuBr 2 , Cu 2 O, CuO, Cu (NO 3 ) · 3H 2 O, CuS, and the like. Although content of the copper compound in a paste is not specifically limited, Usually, about 20 to 70 weight%, Preferably it is about 30 to 60 weight%. The paste usually contains a binder component, and the binder component is preferably a resin component that decomposes in the heat treatment step and is easily removed by washing with water.
上記ペーストとしては、ガラスの着色用ペーストとして市販されているものを用いることができる。例えば、硫酸銅４０〜６０重量％、硫酸ソーダ５〜１５重量％程度、溶剤１５〜２５重量％程度、樹脂成分１〜５重量％程度からなるペーストが挙げられる。 As said paste, what is marketed as a paste for coloring of glass can be used. For example, the paste which consists of about 40 to 60 weight% of copper sulfate, about 5 to 15 weight% of sodium sulfate, about 15 to 25 weight% of solvent, and about 1 to 5 weight% of resin components is mentioned.
ペースト塗布後の乾燥条件は特に限定されず、通常１５０℃〜３００℃程度で５〜１５分程度乾燥すればよい。 The drying conditions after applying the paste are not particularly limited, and may be normally dried at about 150 ° C. to 300 ° C. for about 5 to 15 minutes.
また、銅塩の溶融槽にガラス基材を浸漬する方法では、３００〜７００℃程度の温度であってガラス基材の屈伏点以下の温度に加熱した銅塩の溶融槽中に、ガラス基材を１０分〜２０時間程度浸漬した後、溶融槽から引き上げて水洗すればよい。かかる方法によって、ガラス基材に銅イオンが拡散して該ガラス基材の表面にハロゲン化銅の微結晶層が形成される。 In the method of immersing the glass substrate in the copper salt melting tank, the glass substrate is heated in the copper salt melting tank heated to a temperature of about 300 to 700 ° C. and lower than the yield point of the glass substrate. After being soaked for about 10 minutes to 20 hours, it may be lifted from the melting tank and washed with water. By this method, copper ions diffuse into the glass substrate, and a copper halide microcrystalline layer is formed on the surface of the glass substrate.
銅塩としては、前記同様の銅化合物が使用できる。また、銅塩以外の成分として、ＮａＮＯ３、Ｎａ２ＳＯ４、ＮａＣｌ等を５〜５０重量％程度含有する溶融塩を使用して銅イオンの拡散を促進させてもよい。As the copper salt, the same copper compound as described above can be used. Further, as components other than copper salts, NaNO 3, Na 2 SO 4 , a molten salt such as NaCl which contained about 5 to 50 wt% may be accelerated diffusion of copper ions using.
銀イオンを拡散させる場合には、上記銅化合物の代わりに、ＡｇＮＯ３、ＡｇＣｌ、ＡｇＢｒ、ＡｇＩ、ＡｇＦ、Ａｇ２Ｓ、Ａｇ２ＳＯ４、Ａｇ２Ｏ等の銀化合物を用いればよい。In the case of diffusing silver ions, silver compounds such as AgNO 3 , AgCl, AgBr, AgI, AgF, Ag 2 S, Ag 2 SO 4 , and Ag 2 O may be used instead of the copper compound.
銅イオン及び銀イオンの一方又は両方を拡散させることにより、ガラス基板中にハロゲン化銅（Ｉ）成分及び銀成分が形成され、所望の青紫光遮断ガラスが得られる。 By diffusing one or both of copper ions and silver ions, a copper (I) halide component and a silver component are formed in the glass substrate, and a desired blue-violet light blocking glass is obtained.
本発明の青紫光遮断ガラスは、ハロゲン化銅（Ｉ）微粒子に加えて銀を含有するため、波長４５０〜６００ｎｍの光を十分に透過し、４５０ｎｍよりも短波長の光をシャープに遮断できる。具体的には、好適な実施態様では、厚さ１ｍｍのガラス板に波長３００〜６００ｎｍの光を入射して透過率を測定した際に、４５０〜６００ｎｍの光の平均透過率が８５％以上であり、透過率５０％の値が波長４３２ｎｍ以上に示される。即ち、本発明の青紫光遮断ガラスは、４５０〜６００ｎｍの透過率が高く、且つ、従来品に比して４５０ｎｍ付近でシャープな遮断機能（波長傾斜幅：Δλが小さい）を有する。 Since the blue-violet light blocking glass of the present invention contains silver in addition to the copper (I) halide fine particles, it can sufficiently transmit light having a wavelength of 450 to 600 nm and sharply block light having a wavelength shorter than 450 nm. Specifically, in a preferred embodiment, when light having a wavelength of 300 to 600 nm is incident on a glass plate having a thickness of 1 mm and the transmittance is measured, the average transmittance of light having a wavelength of 450 to 600 nm is 85% or more. Yes, a value of transmittance of 50% is shown at a wavelength of 432 nm or more. That is, the blue-violet light blocking glass of the present invention has a high transmittance of 450 to 600 nm and a sharp blocking function (wavelength gradient width: Δλ is small) near 450 nm as compared with the conventional product.
また、本発明の青紫光遮断ガラスはＣｄ化合物を用いる必要がないため、安全性が高く、製造及び廃棄処理が容易である。 Further, since the blue-violet light blocking glass of the present invention does not require the use of a Cd compound, it is highly safe and easy to manufacture and dispose of.
以下に実施例を示して本発明を具体的に説明する。但し本発明は実施例に限定されない。 The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples.
実施例１〜５及び比較例１〜２
下記表１に示される組成となるようにガラス原料を秤量及び調合した。 Examples 1-5 and Comparative Examples 1-2
The glass raw materials were weighed and prepared so as to have the composition shown in Table 1 below.
比較例１及び２は、ともに従来品であり、参考（比較）のために示す。 Comparative Examples 1 and 2 are both conventional products and are shown for reference (comparison).
比較例１は、ハロゲン化銅（Ｉ）微粒子分散ガラス（銀は含まない）を示す。 Comparative Example 1 shows copper (I) halide fine-particle dispersed glass (not containing silver).
比較例２は、Ｃｄｓ微粒子分散ガラスを示す
原料混合物を、アルミナ坩堝中、１４００℃で溶融、撹拌、清澄した。次に、溶融物を炭素型に流し込み、４０℃／ｈｒの速度で室温まで冷却後、５０℃／ｈｒの速度で昇温し、６３０℃で４５分熱処理後、続けて６００℃で９０分熱処理を行った。Comparative Example 2 shows a Cds fine particle-dispersed glass. A raw material mixture was melted, stirred and clarified at 1400 ° C. in an alumina crucible. Next, the melt is poured into a carbon mold, cooled to room temperature at a rate of 40 ° C./hr, heated at a rate of 50 ° C./hr, heat treated at 630 ° C. for 45 minutes, and subsequently heat treated at 600 ° C. for 90 minutes. Went.
ハロゲン化銅（Ｉ）微粒子及び銀微粒子の平均粒子径は、いずれも８ｎｍであった。 The average particle size of the copper (I) halide fine particles and silver fine particles was 8 nm.
熱処理後、ガラスを切断、研磨することにより厚さ１ｍｍのガラス板を得た。 After the heat treatment, the glass was cut and polished to obtain a glass plate having a thickness of 1 mm.
試験例１
実施例及び比較例で得られたガラス板の分光特性を調べた。 Test example 1
The spectral characteristics of the glass plates obtained in Examples and Comparative Examples were examined.
具体的には、各ガラス板の板面に対して垂直方向から、波長３００〜６００ｎｍの光を照射することにより各波長における透過率を測定した。 Specifically, the transmittance at each wavelength was measured by irradiating light having a wavelength of 300 to 600 nm from a direction perpendicular to the plate surface of each glass plate.
実施例１〜３及び比較例１〜２で作製したガラス板について、波長と透過率（％）との関係を示すグラフを、図１及び図２に分けて示す。また、４５０〜６００ｎｍの光の平均透過率、Δλ及び透過率５０％の波長の各データを下記表２に示す。 About the glass plate produced in Examples 1-3 and Comparative Examples 1-2, the graph which shows the relationship between a wavelength and the transmittance | permeability (%) is divided and shown in FIG.1 and FIG.2. Further, Table 2 below shows each data of average transmittance of light of 450 to 600 nm, Δλ, and wavelength of transmittance of 50%.
実施例４及び５で作製したガラス板については、図示していないが、４５０〜６００ｎｍの光の平均透過率は９０％であり、Δλは１０ｎｍであった。 About the glass plate produced in Examples 4 and 5, although not shown, the average transmittance of light of 450 to 600 nm was 90%, and Δλ was 10 nm.
上記結果からは、本発明のガラス（青紫光遮断ガラス）は、４５０〜６００ｎｍの光の透過率が高く、且つ、従来品に比して、より４５０ｎｍ付近でシャープな遮断能を有することが分かる。他方、比較例１のガラス板は透過率５０％の波長が低波長側にある点で、比較例２のガラス板はΔλの値が大きい点で、分光特性が不十分である。 From the above results, it can be seen that the glass of the present invention (blue-violet light blocking glass) has a high light transmittance of 450 to 600 nm and has a sharp blocking ability near 450 nm as compared with conventional products. . On the other hand, the glass plate of Comparative Example 1 has insufficient spectral characteristics in that the wavelength of 50% transmittance is on the low wavelength side, and the glass plate of Comparative Example 2 has a large Δλ value.
Claims (17)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007545250A JP5142139B2 (en) | 2005-11-15 | 2006-11-15 | Blue-violet light blocking glass |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005330697 | 2005-11-15 | ||
| JP2005330697 | 2005-11-15 | ||
| JP2007545250A JP5142139B2 (en) | 2005-11-15 | 2006-11-15 | Blue-violet light blocking glass |
| PCT/JP2006/322706 WO2007058185A1 (en) | 2005-11-15 | 2006-11-15 | Blue-violet light blocking glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2007058185A1 JPWO2007058185A1 (en) | 2009-04-30 |
| JP5142139B2 true JP5142139B2 (en) | 2013-02-13 |
Family
ID=38048570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007545250A Active JP5142139B2 (en) | 2005-11-15 | 2006-11-15 | Blue-violet light blocking glass |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US7951733B2 (en) |
| EP (1) | EP1953122A4 (en) |
| JP (1) | JP5142139B2 (en) |
| WO (1) | WO2007058185A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009008953B4 (en) * | 2009-02-13 | 2010-12-30 | Schott Ag | X-ray opaque barium-free glass and its use |
| DE102009008954B4 (en) * | 2009-02-13 | 2010-12-23 | Schott Ag | X-ray opaque barium-free glass and its use |
| JP5569942B2 (en) * | 2009-10-27 | 2014-08-13 | 学校法人東京理科大学 | Luminescent glass, light-emitting device provided with the luminescent glass, and method for producing the luminescent glass |
| CN103403906A (en) * | 2011-02-03 | 2013-11-20 | 默克专利股份有限公司 | Photovoltaic cells |
| JP5997918B2 (en) * | 2012-03-30 | 2016-09-28 | 株式会社Ｎｂｃメッシュテック | Ultraviolet shielding material and method for producing ultraviolet shielding material |
| JP6512813B2 (en) * | 2014-12-15 | 2019-05-15 | 積水化成品工業株式会社 | Optical film and its use |
| US10150692B2 (en) * | 2015-12-18 | 2018-12-11 | Corning Incorporated | Photochromic glass with sharp cutoff |
| WO2018021223A1 (en) * | 2016-07-29 | 2018-02-01 | 旭硝子株式会社 | Near-infrared cut filter glass |
| JP7024711B2 (en) * | 2016-07-29 | 2022-02-24 | Ａｇｃ株式会社 | Optical glass and near infrared cut filter |
| DE102019126332A1 (en) * | 2019-09-30 | 2021-04-01 | Schott Ag | Glass articles, processes for their manufacture and uses |
| JP7429622B2 (en) * | 2020-08-26 | 2024-02-08 | 株式会社オハラ | Optical glass manufacturing method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3208860A (en) * | 1962-07-31 | 1965-09-28 | Corning Glass Works | Phototropic material and article made therefrom |
| JPH05105865A (en) * | 1991-03-18 | 1993-04-27 | Isuzu Seiko Glass Kk | Ultraviolet screening material |
| JPH06191878A (en) * | 1992-10-30 | 1994-07-12 | Corning Inc | Colored glass and its preparation |
| JPH08259261A (en) * | 1994-11-07 | 1996-10-08 | Corning Inc | Glass article containing silver halide and its production |
| WO2002036512A1 (en) * | 2000-10-27 | 2002-05-10 | Corning S.A. | Non-photochromic, colored, borosilicate inorganic glasses which absorb ultraviolet, and preparations |
| JP2003261357A (en) * | 2002-01-24 | 2003-09-16 | Corning Inc | Method of making polarizing glass |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5056410A (en) * | 1973-09-20 | 1975-05-17 | ||
| US4018965A (en) * | 1975-04-14 | 1977-04-19 | Corning Glass Works | Photochromic sheet glass compositions and articles |
| GB1515641A (en) * | 1976-01-30 | 1978-06-28 | Pilkington Brothers Ltd | Photochromic glasses |
| US4102396A (en) * | 1977-06-23 | 1978-07-25 | Union Oil Company Of California | Determining residual oil saturation following flooding |
| DE3206958C2 (en) * | 1982-02-26 | 1986-09-18 | Schott Glaswerke, 6500 Mainz | Phototropic glass with a refractive index? 1.59, an Abbe number? 44 and a density ≦ 3.0 g / cm? 3? |
| JPS60264344A (en) * | 1984-06-12 | 1985-12-27 | Nippon Sheet Glass Co Ltd | Halide glass for infrared transmission |
| JP2539062B2 (en) * | 1989-12-18 | 1996-10-02 | ホーヤ株式会社 | Multi-component glass containing semiconductor crystallites |
| JP2852462B2 (en) | 1990-04-10 | 1999-02-03 | 五鈴精工硝子 株式会社 | Tinted glass |
| JPH0794334B2 (en) | 1991-03-04 | 1995-10-11 | 五鈴精工硝子株式会社 | Tinted glass |
| JPH05201746A (en) | 1992-01-28 | 1993-08-10 | Isuzu Seiko Glass Kk | Ultraviolet cutoff glass |
| JPH0624794A (en) | 1992-07-08 | 1994-02-01 | Asahi Glass Co Ltd | Production of ultraviolet-shielding glass |
| US5432635A (en) * | 1992-09-29 | 1995-07-11 | Matsushita Electric Industrial Co., Ltd. | Nonlinear optical material and method of manufacturing the same |
| JPH0748140A (en) | 1993-08-04 | 1995-02-21 | Asahi Glass Co Ltd | Production of glass sharply cutting ultraviolet rays |
| JP3049379B2 (en) | 1995-06-08 | 2000-06-05 | 五鈴精工硝子株式会社 | Base glass for ultraviolet shielding glass, and method for producing ultraviolet shielding glass |
| CA2278518A1 (en) * | 1997-02-03 | 1998-08-06 | Yves A.H. Brocheton | Improved photochromic glasses |
| FR2857354B1 (en) * | 2003-07-07 | 2005-09-16 | Centre Nat Rech Scient | VITREOUS COMPOSITION OF VITROCERAMIC TYPE, TRANSPARENT IN THE INFRARED |
| JP2005206434A (en) | 2004-01-23 | 2005-08-04 | Okamoto Glass Co Ltd | Manufacturing process of microparticle dispersion glass and ultraviolet cut filter |
-
2006
- 2006-11-15 WO PCT/JP2006/322706 patent/WO2007058185A1/en active Application Filing
- 2006-11-15 US US12/084,765 patent/US7951733B2/en active Active
- 2006-11-15 EP EP06832637A patent/EP1953122A4/en not_active Withdrawn
- 2006-11-15 JP JP2007545250A patent/JP5142139B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3208860A (en) * | 1962-07-31 | 1965-09-28 | Corning Glass Works | Phototropic material and article made therefrom |
| JPH05105865A (en) * | 1991-03-18 | 1993-04-27 | Isuzu Seiko Glass Kk | Ultraviolet screening material |
| JPH06191878A (en) * | 1992-10-30 | 1994-07-12 | Corning Inc | Colored glass and its preparation |
| JPH08259261A (en) * | 1994-11-07 | 1996-10-08 | Corning Inc | Glass article containing silver halide and its production |
| WO2002036512A1 (en) * | 2000-10-27 | 2002-05-10 | Corning S.A. | Non-photochromic, colored, borosilicate inorganic glasses which absorb ultraviolet, and preparations |
| JP2003261357A (en) * | 2002-01-24 | 2003-09-16 | Corning Inc | Method of making polarizing glass |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1953122A4 (en) | 2010-01-20 |
| US7951733B2 (en) | 2011-05-31 |
| US20090163343A1 (en) | 2009-06-25 |
| JPWO2007058185A1 (en) | 2009-04-30 |
| EP1953122A1 (en) | 2008-08-06 |
| WO2007058185A1 (en) | 2007-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5142139B2 (en) | Blue-violet light blocking glass | |
| JP7084880B2 (en) | Transparent near infrared shielding glass ceramic | |
| JP7291705B2 (en) | Multicolor article and method for producing same | |
| JP7429189B2 (en) | glass ceramic and glass | |
| US10370291B2 (en) | Articles including glass and/or glass-ceramics and methods of making the same | |
| CN1048474C (en) | High-index glasses that ahsorb UV radiation | |
| CA1075064A (en) | Method of rendering surface of lens phototropic | |
| JP2022507157A (en) | Glass-ceramic devices and methods with adjustable infrared transmittance | |
| WO2020196171A1 (en) | Li2o-al2o3-sio2-based crystallized glass | |
| JP2628014B2 (en) | Polarized glass | |
| EP3390314B1 (en) | Photochromic glass with sharp uv cutoff | |
| JP5870087B2 (en) | Red colored glass and method for producing the same | |
| JP2645923B2 (en) | UV blocking material | |
| JPWO2017094869A1 (en) | Glass | |
| EP0881995B9 (en) | Strong uv absorbing glass | |
| JP5100741B2 (en) | UV blocking glass | |
| JP4626934B2 (en) | LCD protective glass | |
| JP2852462B2 (en) | Tinted glass | |
| CN116057023A (en) | Li 2 O－Al 2 O 3 －SiO 2 Crystallizing glass | |
| JP4740924B2 (en) | Modification method of UV blocking glass | |
| Kavei et al. | Oxide glasses doped with silver nanoparticles: properties and technologies | |
| JPH0794334B2 (en) | Tinted glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090713 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090710 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120515 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20120629 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121023 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151130 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5142139 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |